Method for manufacture of faujasite zeolite including zeolite y in the presence of odso

ABSTRACT

The present disclosure is directed to a method of manufacture of faujasite zeolite including zeolite Y. A sol-gel formulation includes a water-soluble fraction of ODSO as an additional component. The resulting products include faujasite zeolite, and yields can be increased relative to comparable sol-gel formulations without ODSO.

FIELD OF THE DISCLOSURE

The present invention relates to methods of making faujasite zeolitesincluding zeolite Y.

BACKGROUND OF THE DISCLOSURE Zeolites

Zeolites are crystalline solids possessing well-defined structures anduniform pore sizes that can be measured in angstroms (Å). Typically,zeolites comprise framework atoms such as silicon, aluminum and oxygenarranged as silica and alumina tetrahedra. Zeolites are generallyhydrated aluminum silicates that can be made or selected with acontrolled porosity and other characteristics, and typically containcations, water and/or other molecules located in the porous network.Hundreds of natural and synthetic zeolite framework types exist with awide range of applications. Numerous zeolites occur naturally and areextensively mined, whereas a wealth of interdependent research hasresulted in an abundance of synthetic zeolites of different structuresand compositions. The unique properties of zeolites and the ability totailor zeolites for specific applications has resulted in the extensiveuse of zeolites in industry as catalysts, molecular sieves, adsorbents,ion exchange materials and for the separation of gases. Certain types ofzeolites find application in various processes in petroleum refineriesand many other applications. The zeolite pores can form sites forcatalytic reactions, and can also form channels that are selective forthe passage of certain compounds and/or isomers to the exclusion ofothers. Zeolites can also possess an acidity level that enhances itsefficacy as a catalytic material or adsorbent, alone or with theaddition of active components.

Zeolite Y (also known as Na—Y zeolite or Y-type faujasite zeolite) is awell known material for its zeolites have ion-exchange, catalytic andadsorptive properties. Zeolite Y is also a useful starting material forproduction of other zeolites such as ultra-stable y-type zeolite (USY).Like typical zeolites, faujasite is synthesized from alumina and silicasources, dissolved in a basic aqueous solution and crystallized. Thefaujasite zeolite has a framework designated as FAU by the InternationalZeolite Association, and are formed by 12-ring structures and havechannels of about 7.4 angstroms (Å). Faujasite zeolites arecharacterized by a 3-dimensional pore structure with pores runningperpendicular to each other in the x, y, and z planes. Secondarybuilding units can be positioned at 4, 6, 6-2, 4-2, 1-4-4 or 6-6. Anexample SAR range for faujasite zeolite is about 2 to about 6, typicallywith a unit cell size (units a, b and c) in the range of about 24.25 to24.85 Å. Faujasite zeolites are typically considered X-type when thesilica-to-alumina ratio (SAR) is at about 2-3, and Y-type when the SARis greater than about 3, for instance about 3-6. The faujasite is in itssodium form and can be ion exchanged with ammonium, and the ammoniumform can be calcined to transform the zeolite to its proton form.

ODSO

Within a typical refinery, there are by-product streams that must betreated or otherwise disposed of. The mercaptan oxidation process,commonly referred to as the MEROX process, has long been employed forthe removal of the generally foul smelling mercaptans found in manyhydrocarbon streams and was introduced in the refining industry overfifty years ago. Because of regulatory requirements for the reduction ofthe sulfur content of fuels for environmental reasons, refineries havebeen, and continue to be faced with the disposal of large volumes ofsulfur-containing by-products. Disulfide oil (DSO) compounds areproduced as a by-product of the MEROX process, in which the mercaptansare removed from any of a variety of petroleum streams includingliquefied petroleum gas, naphtha, and other hydrocarbon fractions. It iscommonly referred to as a ‘sweetening process’ because it removes thesour or foul smelling mercaptans present in crude petroleum. The term“DSO” is used for convenience in this description and in the claims, andwill be understood to include the mixture of disulfide oils produced asby-products of the mercaptan oxidation process. Examples of DSO includedimethyldisulfide, diethyldisulfide, and methylethyldisulfide.

The by-product DSO compounds produced by the MEROX unit can be processedand/or disposed of during the operation of various other refinery units.For example, DSO can be added to the fuel oil pool at the expense of aresulting higher sulfur content of the pool. DSO can be processed in ahydrotreating/hydrocracking unit at the expense of higher hydrogenconsumption. DSO also has an unpleasant foul or sour smell, which issomewhat less prevalent because of its relatively lower vapor pressureat ambient temperature; however, problems exist in the handling of thisoil.

Commonly owned U.S. Pat. No. 10,807,947 which is incorporated byreference herein in its entirety discloses a controlled catalyticoxidation of MEROX process by-products DSO. The resulting oxidizedmaterial is referred to as oxidized disulfide oil (ODSO). As disclosedin 10,807,947, the by-product DSO compounds from the mercaptan oxidationprocess can be oxidized, preferably in the presence of a catalyst. Theoxidation reaction products constitute an abundant source of ODSOcompounds, sulfoxides, sulfonates, sulfinates and sulfones.

The ODSO stream so-produced contains ODSO compounds as disclosed in U.S.Pat. Nos. 10,781,168 and 11,111,212 as compositions (such as a solvent),in U.S. Pat. No. 10,793,782 as an aromatics extraction solvent, and inU.S. Pat. No. 10,927,318 as a lubricity additive, all of which areincorporated by reference herein in their entireties. In the event thata refiner has produced or has on hand an amount of DSO compounds that isin excess of foreseeable needs for these or other uses, the refiner maywish to dispose of the DSO compounds in order to clear a storage vesseland/or eliminate the product from inventory for tax reasons.

Thus, there is a clear and long-standing need to provide an efficientand economical process for the treatment of the large volumes of DSOby-products and their derivatives to effect and modify their propertiesin order to facilitate and simplify their environmentally acceptabledisposal, and to utilize the modified products in an economically andenvironmentally friendly manner, and thereby enhance the value of thisclass of by-products to the refiner.

Despite the known ways to produce faujasite zeolites including zeoliteY, there remains a need in the art for improved methods to producezeolite materials, in particular using DSO by-products in aneconomically and environmentally friendly manner. It is in regard tothese and other problems in the art that the present disclosure isdirected to provide a technical solution for an effective method ofmanufacturing zeolite Y.

SUMMARY OF THE DISCLOSURE

A method for the preparation of faujasite zeolite is provided. Themethod comprises: forming a homogeneous aqueous mixture of a silicasource, an aluminum source, an alkali metal source, water and aneffective amount of water-soluble oxidized disulfide oil (ODSO); andheating the homogeneous aqueous mixture under conditions and for a timeeffective to form a precipitate suspended in a supernatant as anintermediate suspension, wherein the precipitate comprises faujasitezeolite.

In certain embodiments, a cumulative amount of ODSO and water isapproximately equivalent to an amount of water that is effective toproduce faujasite zeolite in the absence of ODSO; the cumulative amountof ODSO and water, an amount of the silica source, an amount of thealuminum source, and an amount of the alkali metal source are providedat an ODSO-enhanced compositional ratio; the ODSO-enhanced compositionalratio is approximately equivalent to a baseline compositional ratio ofwater, silica, aluminum and alkali metal that is effective to producefaujasite zeolite in the absence of ODSO; and the conditions and time ofheating are approximately equivalent to those that are effective toproduce faujasite zeolite in the absence of ODSO. In certainembodiments, faujasite zeolite is recovered and is characterized by azeolite yield, and wherein the zeolite yield is greater than a zeoliteyield for a comparable faujasite zeolite formed from the baselinecompositional ratio of components. In certain embodiments, the faujasitezeolite is zeolite Y. In certain embodiments, the effective amount ofODSO is less than the amount of ODSO that produces only amorphousalumina or silica-alumina. In certain embodiments, the alkali metalsource is sodium and the mass ratio of ODSO to sodium is in the range ofabout 0.1-2.5. In certain embodiments, the faujasite zeolite is zeoliteX.

In certain embodiments, the ODSO is derived from oxidation of disulfideoil compounds present in an effluent refinery hydrocarbon streamrecovered following catalytic oxidation of mercaptans present in amercaptan-containing hydrocarbon stream. In certain embodiments, theODSO compounds have 3 or more oxygen atoms and include one or morecompounds selected from the group consisting of (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR), wherein R and R′ are alkyl or aryl groups comprising1-10 carbon atoms and wherein X denotes esters and is (R—SO) or (R—SOO).In certain embodiments, the ODSO compounds have 3 or more oxygen atomsand include two or more compounds selected from the group consisting of(R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR), wherein R and R′ are alkyl oraryl groups comprising 1-10 carbon atoms and wherein X denotes estersand is (R—SO) or (R—SOO). In certain embodiments, the ODSO compoundshave 3 or more oxygen atoms and include one or more compounds selectedfrom the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), wherein Rand R′ are alkyl or aryl groups comprising 1-10 carbon atoms.

Any combinations of the various embodiments and implementationsdisclosed herein can be used. These and other aspects and features canbe appreciated from the following description of certain embodiments andthe accompanying drawings and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a simplified schematic diagram of a generalized version of aconventional mercaptan oxidation or MEROX process for the liquid-liquidextraction of a mercaptan containing hydrocarbon stream.

FIG. 2 is a simplified schematic diagram of a generalized version of anenhanced mercaptan oxidation or E-MEROX process.

FIG. 3A is the experimental ¹H-NMR spectrum of the polar, water-solubleODSO fraction used in an example herein.

FIG. 3B is the experimental ¹³C-DEPT-135-NMR spectrum of the polar,water-soluble ODSO fraction used in an example herein.

FIG. 4 shows X-ray diffraction patterns of the as-made products (priorto calcination) from the Examples 1-4.

FIG. 5 is a plot of ODSO/Na ratios against ODSO mass demonstratingtransition between crystalline products and amorphous products.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE DISCLOSURE

The present disclosure is directed to a method of manufacture offaujasite zeolites including zeolite Y. This is accomplished by using animproved sol-gel formulation including a water-soluble fraction of ODSOas an additional component. The resulting products include faujasitezeolites such as zeolite Y. In certain embodiments yields are increasedrelative to comparable sol-gel formulations without ODSO as a precursor.

In conventional synthesis of faujasite zeolites, water is used as anaqueous medium and as a solvent. In the embodiments of the presentdisclosure, an effective amount of water-soluble ODSO compounds is addedwithin a homogeneous aqueous mixture. In certain embodiments, the ODSOis derived from a sulfur-containing refinery waste stream of disulfideoil and is used as a component for the synthesis of faujasite zeolitesincluding zeolite Y.

In certain embodiments the overall zeolite yield is increased using ODSOprecursors as an additional component compared with an approximatelyequivalent water-only synthesis for faujasite zeolite. In certainembodiments, compared with an approximately equivalent water-onlysynthesis for zeolite Y, the use of ODSO compounds in the synthesesherein increases the overall zeolite yield by about 0.5-15, 0.5-12,0.5-10, 1-15, 1-12 or 1-10 mass %. In certain embodiments, compared withan approximately equivalent water-only synthesis for zeolite Y, the useof ODSO compounds in the syntheses herein increases the overall productyield (crystalline and amorphous product) by about 0.5-40, 0.5-30,0.5-20, 0.5-15, 1-40, 1-30, 1-20 or 1-15 mass %.

Synthesis Steps

Methods for the preparation of faujasite zeolites including zeolite Yare provided. Effective amounts and proportions of precursors andreagents are formed as a homogeneous aqueous mixture, including a watersource, an aluminum source, a silica source and an alkali metal source.In the place of a certain amount of water, an effective amount ofwater-soluble ODSO is used as an additional component. The componentsare mixed for an effective time and under conditions suitable to formthe homogeneous aqueous mixture. The chronological sequence of mixingcan vary, with the objective being a highly homogenous distribution ofthe components in an aqueous mixture. The homogeneous aqueous mixture isheated under conditions and for a time effective to form a precipitate(product) suspended in a supernatant (mother liquor). The precipitate isrecovered, for example by filtration, washing and drying, as porousfaujasite zeolite such as zeolite Y.

An effective amount of water for the aqueous environment and as asolvent during the sol-gel process can be provided from one or morewater sources, including utility water that is added to form thehomogeneous aqueous mixture, a water-containing silica source such ascolloidal silica, an aqueous mixture of an aluminum oxide source, and/oran aqueous mixture of an alkali metal source. These mixture componentsare added with water to the reaction vessel prior to heating. Typically,water allows for adequate mixing to realize a more homogeneousdistribution of the sol-gel components, which ultimately produces a moredesirable product because each crystal is more closely matched inproperties to the next crystal. Insufficient mixing could result inundesirable “pockets” of highly concentrated sol-gel components and thismay lead to impurities in the form of different structural phases ormorphologies. Water also determines the yield per volume. In thedescriptions that follow, it is understood that water is a component ofhomogeneous aqueous mixtures from one or more of the sources of water.

In certain embodiments, a homogeneous aqueous mixture is formed by:providing a silica source; combining an aluminum oxide source and analkali metal source; and combining an effective amount of water-solubleODSO. Alternatively, the water-soluble ODSO is combined with thealuminum oxide source and the alkali metal source, and that mixture iscombined with the silica source.

In certain embodiments, a homogeneous aqueous mixture is formed by:providing an aluminum oxide source and an alkali metal source as amixture; combining a silica source; and combining an effective amount ofwater-soluble ODSO. Alternatively, the water-soluble ODSO is combinedwith the silica source, and that mixture is combined with the aluminumoxide source and the alkali metal source.

In certain embodiments, a homogeneous aqueous mixture is formed by:combining an effective amount of water-soluble ODSO with a silica sourceto form a mixture; and that mixture is combined with an aluminum oxidesource and an alkali metal source.

In certain embodiments, a homogeneous aqueous mixture is formed by:combining an effective amount of the water-soluble ODSO with thealuminum oxide source and the alkali metal source to form a mixture; andthat mixture is combined with the silica source.

A homogeneous aqueous mixture of the aluminum source, silica source,alkali source and ODSO is formed from any of the above chronologicalsequences of component addition. The homogeneous aqueous mixture isheated under conditions and for a time effective to form a precipitatesuspended in a supernatant, wherein the time and conditions areeffective to realize faujasite zeolite such as zeolite Y as theprecipitate, which is recovered, for example by filtration, washing anddrying. In certain embodiments the recovered precipitate is calcined ata suitable temperature, temperature ramp rate and for a suitable periodof time.

It is to be appreciated by those skilled in the art that in certainembodiments effective baseline compositional ratios for synthesis ofzeolites including faujasite zeolite such as zeolite Y as disclosedherein can be determined by empirical data, for instance summarized asphase boundary diagrams or other methodologies as is known in materialsynthesis.

In certain embodiments, effective ratios of precursors and reagents forproduction of zeolite Y are within those that are known to produce suchzeolites and can be determined by those of ordinary skill in the art.For example, effective amounts of silica and alumina precursors areprovided to produce zeolite Y having a silica-to-alumina ratio (SAR) inthe range of about 3-6, 3-5, 3-4.5 or 3-4. In certain embodiments,ratios of materials effective to synthesize zeolite Y as disclosedherein are similar to those used in typical synthesis of zeolite Y inthe absence of ODSO. In certain embodiments, baseline compositionalratios of the aqueous composition used to produce zeolites hereininclude (on a molar basis):

-   -   SiO₂/Al₂O₃: 1-20    -   OH⁻/SiO₂: 0.075-3.0    -   Alkali metal cation/SiO₂: 0.075-3.0    -   H₂O/SiO₂: 5-80        It is appreciated by those skilled in the art that these molar        composition ratios can be expressed on a mass basis. In certain        embodiments, an exemplary baseline compositional ratio effective        to produce zeolite Y is approximately 1Al₂O₃:10SiO₂:8Na₂O:400H₂O        on a molar basis.

In the embodiments herein, ratios of components in homogeneous aqueousmixtures including ODSO are referred to as “ODSO-enhanced compositionalratios.” In certain embodiments an ODSO-enhanced compositional ratio isone in which ODSO is included to replace an approximately equivalentmass of water in the homogeneous aqueous mixture, and wherein acumulative mass of ODSO and water (ODSO+H₂O) is approximately equivalentto a mass of water that is effective to produce faujasite zeolitesincluding zeolite Y in the absence of ODSO. In certain embodiments: abaseline compositional ratio of silica, aluminum, alkali metal and wateris known or determined to be effective to produce faujasite zeolitesincluding zeolite Y in the absence of ODSO; an ODSO-enhancedcompositional ratio is approximately equivalent to the baselinecompositional ratio except for the substitution of ODSO for water on amass basis; and wherein the conditions and time of heating theODSO-enhanced sol-gel is approximately equivalent to those that areeffective to produce the faujasite zeolites including zeolite Y in theabsence of ODSO.

The aluminum source can comprise, without limitation, one or more ofaluminates, alumina, other zeolites, aluminum colloids, boehmites,pseudo-boehmites, aluminum salts such as aluminum nitrate, aluminumsulfate and alumina chloride, aluminum hydroxides and alkoxides,aluminum wire and alumina gels. For example, suitable materials asaluminum sources include commercially available materials including forinstance high purity aluminas (CERALOX commercially available fromSasol) and alumina hydrates (PURAL and CAPITAL commercially availablefrom Sasol), boehmites (DISPERSAL and DISPAL commercially available fromSasol), and silica-alumina hydrates (SIRAL commercially available fromSasol) and the corresponding oxides (SIRALOX commercially available fromSasol).

The silica source can comprise, without limitation, one or more ofsilicates including sodium silicate (water glass), rice husk, fumedsilica, precipitated silica, colloidal silica, silica gels, otherzeolites, dealuminated zeolites, and silicon hydroxides and alkoxides.Silica sources resulting in a high relative yield are preferred. Forinstance, suitable materials as silica sources include fumed silicacommercially available from Cabotand colloidal silica (LUDOXcommercially available from Cabot).

The disclosed process for synthesizing faujasite zeolites includingzeolite Y can occur in the absence or presence of seed materialscomprising zeolite structures such as zeolite Y, zeolite X, USY zeolite,faujasite zeolite or small protozeolitic species (gels). Functions ofthe seeds can include, but are not limited to: supporting growth on thesurface of the seed, that is, where crystallization does not undergonucleation but rather crystal growth is directly on the surface of theseed; the parent gel and seed share common larger composite buildingunits; the parent gel and seed share common smaller units, for instance4 member rings; seeds that undergo partial dissolution to provide asurface for crystal growth of a zeolite; crystallization occurs througha “core-shell” mechanism with the seed acting as a core and the targetmaterial grows on the surface; and/or where the seeds partially dissolveproviding essential building units that can orientate zeolitecrystallization.

A hydroxide mineralizer is included as the hydroxide derived from thealkali metal source from the Periodic Table IUPAC Group 1 alkalinemetals (and/or from the hydroxide of any hydroxide-containing structuredirecting agent). For example these are selected from the groupconsisting of NaOH, KOH, RbOH, LiGH, CsOH and combinations thereof. Incertain embodiments a Na-based hydroxide mineralizer is selected. Notethat the alkali metal source is provide as a hydroxide, but inembodiments herein where the ratio is expressed based on the mass of thealkali, it is the metal itself. For instance, when the alkali is NaOH,the ODSO/Na ratio is determined by dividing the mass of the ODSO by themass of the Na portion of NaOH, that is, about 57.5% of the NaOH mass.In certain embodiments the basic components from the hydroxidemineralizer source are provided in effective amounts so as to maintainthe homogeneous mixture at a pH level of greater than or equal to about9, for example in the range of about 9-14, 9-13, 10-14, 10-13, 11-14 or11-13. It is appreciated that the overall pH is influenced by anionsfrom the hydroxide mineralizer source, and in certain embodiments anionsfrom other sources such as from an alumina source or a silica source. Incertain embodiments hydroxide anions are provided as the mineralizerfrom an alkali metal source and a structure directing agent. In theprocess herein, the pH is reduced by the presence of ODSO, therefore,the quantity of the basic compound from one or more of theaforementioned sources can be adjusted accordingly to attain therequisite pH.

The mixing steps typically occur at ambient temperature and pressure(for instance about 20° C. and about 1 standard atmosphere), for amixing time that is sufficient to realize a homogeneous distribution ofthe components. In certain embodiments the sol-gel can be aged beforebeing subjected to subsequent hydrothermal treatment, for example for aperiod of about 0-48, 0-24, 0-5, 0.5-48, 0.5-24 or 0.5-5 hours.Hydrothermal treatment is then carried out at a temperature in the rangeof about 90-180, 90-150, 100-180 or 100-150° C. and at atmospheric orautogenous pressure (from the sol-gel or from the sol-gel plus anaddition of a gas purge into the vessel prior to heating), and for atime period within the range of about 0.1-3, 0.2-3, 0.1-2, 0.2-2, 0.1-1or 0.2-1 day, to ensure crystallization and formation of a zeolite gel.

The products are washed, for example with water at a suitable quantity,for example at about twice the volume of the sol-gel solution. The washcan be at a temperature of from about 20-80° C., at atmospheric, vacuumor under pressure. The wash can continue until the pH of the filtrateapproaches about 7-9. The solids are recovered by filtration, forinstance, using known techniques such as centrifugation, gravity, vacuumfiltration, filter press, or rotary drums, and dried, for example at atemperature of up to about 110 or 150° C.

In certain optional embodiments, if the as-made faujasite zeolitesincluding zeolite Y are calcined, conditions for calcination can includetemperatures in the range of about 450-700, 450-600, 500-700 or 500-600°C., atmospheric pressure, and a time period of about 3-24, 3-18, 6-24 or6-18 hours. Calcining can occur with ramp rates in the range of fromabout 0.1-10, 0.1-5, 0.1-3, 1-10, 1-5 or 1-3° C. per minute. In certainembodiments calcination can have a first step ramping to a temperatureof between about 100-150° C. with a holding time of from about 2-24hours (at ramp rates of from about 0.1-5, 0.1-3, 1-5 or 1-3° C. per min)before increasing to a higher temperature with a final holding time inthe range of about 2-24 hours.

ODSO

Example embodiments of the present disclosure are directed to one ormore ODSO compounds that are used as additional components in ahomogeneous aqueous mixture for zeolite synthesis. The additionalcomponents can be a mixture that comprises two or more ODSO compounds.In the description herein, the terms “oxidized disulfide oil”, “ODSO”,“ODSO mixture” and “ODSO compound(s)” may be used interchangeably forconvenience. As used herein, the abbreviations of oxidized disulfideoils (“ODSO”) and disulfide oils (“DSO”) will be understood to refer tothe singular and plural forms, which may also appear as “DSO compounds”and “ODSO compounds,” and each form may be used interchangeably. Incertain instances, a singular ODSO compound may also be referenced.

In the process herein, an effective amount of one or more ODSO compoundsare used in the synthesis of faujasite zeolite including zeolite Y. Incertain embodiments an effective amount can be based on an amount thatattains a desired pH range. In certain embodiments an effective amountcan be approximately equivalent to a reduction in the amount of waterthat is used in the homogeneous aqueous mixture compared to synthesiswithout ODSO. In certain embodiments an effective amount can be based ona ratio of ODSO to alkali metal. In certain embodiments a ratio of ODSOto alkali metal represents the amount of ODSO relative to the amount ofthe selected alkali metal on a mass/mass basis or a molar/molar basis.For example, if sodium is used the ratio is expressed as ODSO/Na on amass/mass basis or a molar/molar basis. In certain embodiments, theeffective amount of ODSO is that which results in a pH level of greaterthan or equal to about 9, for example in the range of about 9-14, 9-13,10-15, 10-14, 10-13, 11-14 or 11-13 in the homogeneous aqueous mixture.In certain embodiments, the effective amount of ODSO can be relative tothe quantity of basic groups in the homogeneous aqueous mixture, such asOH⁻, to attain a desired pH range, with basic group contributions fromthe alkali metal source; such a ratio can be expressed on a molar basisor on a mass basis. In certain embodiments, the effective amount of ODSOis that which results in a product that is at least about 0.1 mass % offaujasite zeolite including zeolite Y. In certain embodiments, amorphousalumina or silica alumina is produced as a co-product, and the effectiveamount of ODSO is less than that which produces 100 mass % amorphoussilica alumina. For instance, in the examples provided herein using theselected materials and ratios of silica, alumina and alkali metal, andunder the recited conditions, 100% zeolite Y is produced when theODSO/Na ratio is about 0.9, 1.5 and 1.9, and zeolite Y in combinationwith amorphous alumina or silica alumina is produced when the ODSO/Naratio is about 2.3. In certain embodiments, the effective amount of ODSOis that which results in the synthesis of zeolite Y is an ODSO/Na ratio(wt./wt.) in the range of about 0.1-2.5, 0.1-2.3, 0.1-1.8 or 0.1-0.9. Incertain embodiments, the effective amount of ODSO as expressed asODSO/Na mass ratio ranges is based on a precursor ratio of1Al₂O₃:10SiO₂:8Na₂O:400H₂O on a molar basis, which can be converted to amass basis.

In certain embodiments, the ODSO compounds used as the additionalcomponent used herein is derived from controlled catalytic oxidation ofdisulfide oils from mercaptan oxidation processes. The effluents fromcontrolled catalytic oxidation of disulfide oils from mercaptanoxidation processes includes ODSO compounds and in certain embodimentsDSO compounds that were unconverted in the oxidation process. In certainembodiments this effluent contains water-soluble compounds andwater-insoluble compounds. The effluent contains at least one ODSOcompound, or a mixture of two or more ODSO compounds, selected from thegroup consisting of compounds having the general formula (R—SO—S—R′),(R—SOO—S—R′), (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR). In certain embodiments, in the above formulae R and R′are alkyl or aryl groups comprising 1-10 carbon atoms. Further, Xdenotes esters and is (R—SO) or (R—SOO), with R as defined above. Itwill be understood that since the source of the DSO is a refineryfeedstream, the R and X substituents vary, e.g., methyl and ethylsubgroups, and the number of sulfur atoms, S, in the as-receivedfeedstream to oxidation can extend to 3, for example, trisulfidecompounds.

In certain embodiments the water-soluble compounds and water-insolublecompounds are separated from one another, and a component used hereinfor zeolite synthesis comprises all or a portion of the water-solublecompounds separated from the total effluents from oxidation of disulfideoils from mercaptan oxidation processes. For example, the differentphases can be separated by decantation or partitioning with a separatingfunnel, separation drum, by decantation, or any other known apparatus orprocess for separating two immiscible phases from one another. Incertain embodiments, the water-soluble and water-insoluble componentscan be separated by distillation as they have different boiling pointranges. It is understood that there will be crossover of thewater-soluble and water-insoluble components in each fraction due tosolubility of components, typically in the ppmw range (for instance,about 1-10,000, 1-1,000, 1-500 or 1-200 ppmw). In certain embodiments,contaminants from each phase can be removed, for example by stripping oradsorption.

In certain embodiments a component used herein for zeolite synthesiscomprises, consists of or consists essentially of at least onewater-soluble ODSO compound having 3 or more oxygen atoms that isselected from the group consisting of compounds having the generalformula (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR). In certain embodiments acomponent used herein for zeolite synthesis comprises, consists of orconsists essentially of a mixture or two or more water-soluble ODSOcompounds having 3 or more oxygen atoms, that is selected from the groupconsisting of compounds having the general formula (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR). In certain embodiments a component used herein forzeolite synthesis comprises, consists of or consists essentially of ODSOcompounds selected from the group consisting of (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH),(R—SOO—SO—OH), and mixtures thereof. In certain embodiments, in theabove formulae R and R′ are alkyl or aryl groups comprising 1-10 carbonatoms. Further, X denotes esters and is (R—SO) or (R—SOO), with R asdefined above. In certain embodiments, the R and R′ are methyl and/orethyl groups. In certain embodiments, the ODSO compound(s) used hereinas a component for zeolite synthesis have 1 to 20 carbon atoms.

In certain embodiments, a component used herein for zeolite synthesiscomprises, consists of or consists essentially of ODSO compounds havingan average density greater than about 1.0 g/cc. In certain embodiments,a component used herein for zeolite synthesis comprises, consists of orconsists essentially of ODSO compounds having an average boiling pointgreater than about 80° C. In certain embodiments, a component usedherein for zeolite synthesis comprises, consists of or consistsessentially of ODSO compounds having a dielectric constant that is lessthan or equal to 100 at 0° C.

Table 1 includes examples of polar water-soluble ODSO compounds thatcontain 3 or more oxygen atoms. In certain embodiments the identifiedODSO compounds are obtained from a water-soluble fraction of theeffluents from oxidation of DSO obtained from MEROX by-products. TheODSO compounds that contain 3 or more oxygen atoms are water-solubleover effectively all concentrations, for instance, with some minoramount of acceptable tolerance for carry over components from theeffluent stream and in the water insoluble fraction with 2 oxygen atomsof no more than about 1, 3 or 5 mass percent.

In certain embodiments the ODSO compounds used as a component forzeolite synthesis comprise all or a portion of the ODSO compoundscontained in an oxidation effluent stream that is obtained by controlledcatalytic oxidation of MEROX process by-products, DSO compounds, asdisclosed in U.S. Pat. Nos. 10,807,947 and 10,781,168 and asincorporated herein by reference above.

In some embodiments, the ODSO compounds used as a component for zeolitesynthesis are derived from oxidized DSO compounds present in an effluentrefinery hydrocarbon stream recovered following the catalytic oxidationof mercaptans present in the hydrocarbon stream. In some embodiments,the DSO compounds are oxidized in the presence of a catalyst.

As noted above, the designation “MEROX” originates from the function ofthe process itself, that is, the conversion of mercaptans by oxidation.The MEROX process in all of its applications is based on the ability ofan organometallic catalyst in a basic environment, such as a caustic, toaccelerate the oxidation of mercaptans to disulfides at near ambienttemperatures and pressures. The overall reaction can be expressed asfollows:

RSH+¼O₂→½RSSR+½H₂O  (1)

where R is a hydrocarbon chain that may be straight, branched, orcyclic, and the chains can be saturated or unsaturated. In mostpetroleum fractions, there will be a mixture of mercaptans so that the Rcan have 1, 2, 3 and up to 10 or more carbon atoms in the chain. Thisvariable chain length is indicated by R and R′ in the reaction. Thereaction is then written:

2R′SH+2RSH+O₂→2R′SSR+2H₂O  (2)

This reaction occurs spontaneously whenever any sour mercaptan-bearingdistillate is exposed to atmospheric oxygen, but proceeds at a very slowrate. In addition, the catalyzed reaction (1) set forth above requiresthe presence of an alkali caustic solution, such as aqueous sodiumhydroxide. The mercaptan oxidation proceeds at an economically practicalrate at moderate refinery downstream temperatures.

The MEROX process can be conducted on both liquid streams and oncombined gaseous and liquid streams. In the case of liquid streams, themercaptans are converted directly to disulfides which remain in theproduct so that there is no reduction in total sulfur content of theeffluent stream. The MEROX process typically utilizes a fixed bedreactor system for liquid streams and is normally employed with chargestocks having end points above 135° C.-150° C. Mercaptans are convertedto disulfides in the fixed bed reactor system over a catalyst, forexample, an activated charcoal impregnated with the MEROX reagent, andwetted with caustic solution. Air is injected into the hydrocarbonfeedstream ahead of the reactor and in passing through thecatalyst-impregnated bed, the mercaptans in the feed are oxidized todisulfides. The disulfides are substantially insoluble in the causticand remain in the hydrocarbon phase. Post treatment is required toremove undesirable by-products resulting from known side reactions suchas the neutralization of H₂S, the oxidation of phenolic compounds,entrained caustic, and others.

The vapor pressures of disulfides are relatively low compared to thoseof mercaptans, so that their presence is much less objectionable fromthe standpoint of odor; however, they are not environmentally acceptabledue to their sulfur content and their disposal can be problematical.

In the case of mixed gas and liquid streams, extraction is applied toboth phases of the hydrocarbon streams. The degree of completeness ofthe mercaptan extraction depends upon the solubility of the mercaptansin the alkaline solution, which is a function of the molecular weight ofthe individual mercaptans, the extent of the branching of the mercaptanmolecules, the concentration of the caustic soda and the temperature ofthe system. Thereafter, the resulting DSO compounds are separated andthe caustic solution is regenerated by oxidation with air in thepresence of the catalyst and reused.

Referring to the attached drawings, FIG. 1 is a simplified schematic ofa generalized version of a conventional MEROX process employingliquid-liquid extraction for removing sulfur compounds. A MEROX unit1010, is provided for treating a mercaptan containing hydrocarbon stream1001. In some embodiments, the mercaptan containing hydrocarbon stream1001 is LPG, propane, butane, light naphtha, kerosene, jet fuel, or amixture thereof. The process generally includes the steps of:introducing the hydrocarbon stream 1001 with a homogeneous catalyst intoan extraction vessel 1005 containing a caustic solution 1002, in someembodiments, the catalyst is a homogeneous cobalt-based catalyst;passing the hydrocarbon catalyst stream in counter-current flow throughthe extraction section of the extraction 1005 vessel in which theextraction section includes one or more liquid-liquid contactingextraction decks or trays (not shown) for the catalyzed reaction withthe circulating caustic solution to convert the mercaptans towater-soluble alkali metal alkane thiolate compounds; withdrawing ahydrocarbon product stream 1003 that is free or substantially free ofmercaptans from the extraction vessel 1005, for instance, having no morethan about 1000, 100, 10 or 1 ppmw mercaptans; recovering a combinedspent caustic and alkali metal alkane thiolate stream 1004 from theextraction vessel 1005; subjecting the spent caustic and alkali metalalkane thiolate stream 1004 to catalyzed wet air oxidation in a reactor1020 into which is introduced catalyst 1005 and air 1006 to provide theregenerated spent caustic 1008 and convert the alkali metal alkanethiolate compounds to disulfide oils; and recovering a by-product stream1007 of DSO compounds and a minor proportion of other sulfides such asmono-sulfides and tri-sulfides. The effluents of the wet air oxidationstep in the MEROX process can comprise a minor proportion of sulfidesand a major proportion of disulfide oils. As is known to those skilledin the art, the composition of this effluent stream depends on theeffectiveness of the MEROX process, and sulfides are assumed to becarried-over material. A variety of catalysts have been developed forthe commercial practice of the process. The efficiency of the MEROXprocess is also a function of the amount of H₂S present in the stream.It is a common refinery practice to install a prewashing step for H₂Sremoval.

An enhanced MEROX process (“E-MEROX”) is a modified MEROX process wherean additional step is added, in which DSO compounds are oxidized with anoxidant in the presence of a catalyst to produce a mixture of ODSOcompounds. The by-product DSO compounds from the mercaptan oxidationprocess are oxidized, in some embodiments in the presence of a catalyst,and constitute an abundant source of ODSO compounds that are sulfoxides,sulfonates, sulfinates, sulfones and their corresponding di-sulfurmixtures. The disulfide oils having the general formula RSSR′ (wherein Rand R′ can be the same or different and can have 1, 2, 3 and up to 10 ormore carbon atoms) can be oxidized without a catalyst or in the presenceof one or more catalysts to produce a mixture of ODSO compounds. Theoxidant can be a liquid peroxide selected from the group consisting ofalkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diarylperoxides, peresters and hydrogen peroxide. The oxidant can also be agas, including air, oxygen, ozone and oxides of nitrogen. If a catalystis used in the oxidation of the disulfide oils having the generalformula RSSR′ to produce the ODSO compounds, it can be a heterogeneousor homogeneous oxidation catalyst. The oxidation catalyst can beselected from one or more heterogeneous or homogeneous catalystcomprising metals from the IUPAC Group 4-12 of the Periodic Table,including Ti, V, Mn, Co, Fe, Cr, Cu, Zn, W and Mo. The catalyst can be ahomogeneous water-soluble compound that is a transition metal containingan active species selected from the group consisting of Mo (VI), W (VI),V (V), Ti (IV), and their combination. In certain embodiments, suitablehomogeneous catalysts include molybdenum naphthenate, sodium tungstate,molybdenum hexacarbonyl, tungsten hexacarbonyl, sodium tungstate andvanadium pentoxide. An exemplary catalyst for the controlled catalyticoxidation of MEROX process by-products DSO is sodium tungstate,Na₂WO₄·2H₂O. In certain embodiments, suitable heterogeneous catalystsinclude Ti, V, Mn, Co, Fe, Cr, W, Mo, and combinations thereof depositedon a support such as alumina, silica-alumina, silica, natural zeolites,synthetic zeolites, and combinations comprising one or more of the abovesupports.

The oxidation of DSO typically is carried out in an oxidation vesselselected from one or more of a fixed-bed reactor, an ebullated bedreactor, a slurry bed reactor, a moving bed reactor, a continuousstirred tank reactor, and a tubular reactor. The ODSO compounds producedin the E-MEROX process generally comprise two phases: a water-solublephase and water-insoluble phase, and can be separated into the aqueousphase containing water-soluble ODSO compounds and a non-aqueous phasecontaining water-insoluble ODSO compounds. The E-MEROX process can betuned depending on the desired ratio of water-soluble to water-insolublecompounds presented in the product ODSO mixture. Partial oxidation ofDSO compounds results in a higher relative amount of water-insolubleODSO compounds present in the ODSO product and a near or almost completeoxidation of DSO compounds results in a higher relative amount ofwater-soluble ODSO present in the ODSO product. Details of the ODSOcompositions are discussed in the U.S. Pat. No. 10,781,168, which isincorporated herein by reference above.

FIG. 2 is a simplified schematic of an E-MEROX process that includesE-MEROX unit 1030. The MEROX unit 1010 unit operates similarly as inFIG. 1 , with similar references numbers representing similarunits/feeds. In FIG. 2 , the effluent stream 1007 from the generalizedMEROX unit of FIG. 1 is treated. It will be understood that theprocessing of the mercaptan containing hydrocarbon stream of FIG. 1 isillustrative only and that separate streams of the products, andcombined or separate streams of other mixed and longer chain productscan be the subject of the process for the recovery and oxidation of DSOto produce ODSO compounds, that is the E-MEROX process. In order topractice the E-MEROX process, apparatus are added to recover theby-product DSO compounds from the MEROX process. In addition, a suitablereactor 1035 add into which the DSO compounds are introduced in thepresence of a catalyst 1032 and an oxidant 1034 and subjecting the DSOcompounds to a catalytic oxidation step to produce the mixed stream 1036of water and ODSO compounds. A separation vessel 1040 is provided toseparate the by-product 1044 from the ODSO compounds 1042.

The oxidation to produce OSDO can be carried out in a suitable oxidationreaction vessel operating at a pressure in the range from about 1-30,1-10 or 1-3 bars. The oxidation to produce OSDO can be carried out at atemperature in the range from about 20-300, 20-150, 20-90, 45-300,15-150 or 45-90° C. The molar feed ratio of oxidizingagent-to-mono-sulfur can be in the range of from about 1:1 to 100:1, 1:1to 30:1 or 1:1 to 4:1. The residence time in the reaction vessel can bein the range of from about 5-180, 5-90, 5-30, 15-180, 15-90 or 5-30minutes. In certain embodiments, oxidation of DSO is carried out in anenvironment without added water as a reagent. The by-products stream1044 generally comprises wastewater when hydrogen peroxide is used asthe oxidant. Alternatively, when other organic peroxides are used as theoxidant, the by-products stream 1044 generally comprises the alcohol ofthe peroxide used. For example, if butyl peroxide is used as theoxidant, the by-product alcohol 1044 is butanol.

In certain embodiments water-soluble ODSO compounds are passed to afractionation zone (not shown) for recovery following their separationfrom the wastewater fraction. The fractionation zone can include adistillation unit. In certain embodiments, the distillation unit can bea flash distillation unit with no theoretical plates in order to obtaindistillation cuts with larger overlaps with each other or,alternatively, on other embodiments, the distillation unit can be aflash distillation unit with at least 15 theoretical plates in order tohave effective separation between cuts. In certain embodiments, thedistillation unit can operate at atmospheric pressure and at atemperature in the range of from 100° C. to 225° C. In otherembodiments, the fractionation can be carried out continuously undervacuum conditions. In those embodiments, fractionation occurs at reducedpressures and at their respective boiling temperatures. For example, at350 mbar and 10 mbar, the temperature ranges are from 80° C. to 194° C.and 11° C. to 98° C., respectively. Following fractionation, thewastewater is sent to the wastewater pool (not shown) for conventionaltreatment prior to its disposal. The wastewater by-product fraction cancontain a small amount of water-insoluble ODSO compounds, for example,in the range of from 1 ppmw to 10,000 ppmw. The wastewater by-productfraction can contain a small amount of water-soluble ODSO compounds, forexample, in the range of from 1 ppmw to 50,000 ppmw, or 100 ppmw to50,000 ppmw. In embodiments where alcohol is the by-product alcohol, thealcohol can be recovered and sold as a commodity product or added tofuels like gasoline. The alcohol by-product fraction can contain a smallamount of water-insoluble ODSO compounds, for example, in the range offrom 1 ppmw to 10,000 ppmw. The alcohol by-product fraction can containa small amount of water-soluble ODSO compounds, for example, in therange of from 100 ppmw to 50,000 ppmw.

Examples

The below examples and data are exemplary. It is to be understood thatother ratios and types of aluminum sources, silica sources, alkalimetals and bases can be used as compared to the examples.

Reference Example: The ODSO mixture used in the Example below wasproduced as disclosed in U.S. Pat. No. 10,781,168, incorporated byreference above, and in particular the fraction referred to therein asComposition 2. Catalytic oxidation a hydrocarbon refinery feedstockhaving 98 mass percent of C1 and C2 disulfide oils was carried out. Theoxidation of the DSO compounds was performed in batch mode under refluxat atmospheric pressure, that is, approximately 1.01 bar. The hydrogenperoxide oxidant was added at room temperature, that is, approximately23° C. and produced an exothermic reaction. The molar ratio ofoxidant-to-DSO compounds (calculated based upon mono-sulfur content) was2.90. After the addition of the oxidant was complete, the reactionvessel temperature was set to reflux at 80° C. for approximately onehour after which the water soluble ODSO was produced (referred to asComposition 2 herein and in U.S. Pat. No. 10,781,168) and isolated afterthe removal of water. The catalyst used in the oxidation of the DSOcompounds was sodium tungstate. The Composition 2, referred to herein as“the selected water soluble ODSO fraction,” was used. FIG. 3A is theexperimental ¹H-NMR spectrum of the polar, water soluble ODSO mixturethat is the selected water soluble ODSO fraction in the example herein.FIG. 3B is the experimental ¹³C-DEPT-135-NMR spectrum of the polar,water soluble ODSO mixture that is the selected water soluble ODSOfraction in the example herein. The selected water soluble ODSO fractionwas mixed with a CD₃OD solvent and the spectrum was taken at 25° C.Methyl carbons have a positive intensity while methylene carbons exhibita negative intensity. The peaks in the 48-50 ppm region belong to carbonsignals of the CD₃OD solvent.

When comparing the experimental ¹³C-DEPT-135-NMR spectrum of FIG. 3B forthe selected water soluble ODSO fraction with a saved database ofpredicted spectra, it was found that a combination of the predictedalkyl-sulfoxidesulfonate (R—SO—SOO—OH), alkyl-sulfonesulfonate(R—SOO—SOO—OH), alkyl-sulfoxidesulfinate (R—SO—SO—OH) andalkyl-sulfonesulfinate (R—SOO—SO—OH) most closely corresponded to theexperimental spectrum. This suggests that alkyl-sulfoxidesulfonate(R—SO—SOO—OH), alkyl-sulfonesulfonate (R—SOO—SOO—OH),alkyl-sulfoxidesulfinate (R—SO—SO—OH) and alkyl-sulfonesulfinate(R—SOO—SO—OH) are major compounds in the selected water soluble ODSOfraction. It is clear from the NMR spectra shown in FIGS. 3A and 3B thatthe selected water soluble ODSO fraction comprises a mixture of ODSOcompounds that form the ODSO composition used in the present examples.

Example 1: Precursors for synthesis of zeolite Y were provided in acomparative example, that is, in the absence of ODSO. Aluminumisopropoxide (0.8677 g) was weighed into a polytetrafluoroethylene(PTFE) liner (45 ml). Thereafter, 2.6679 g of a 50 wt. % sodiumhydroxide solution and water (11.7745 g) were added and the mixture wasstirred until the aluminum source dissolved. The silica source, (3.1256g, 40 wt. %), was added and the mixture stirred until homogeneous. Themixture was left to age for 24 hours at room temperature (20° C.) underconstant stirring. The PTFE liner was positioned within an autoclave andtransferred to an oven and heated to a temperature of 100° C. whilstrotating the autoclave. The autoclave was kept at isothermal conditionsfor 12 hours. Thereafter, the product was washed with distilled waterand dried. The dry mass was 0.9083 g, and was determined to be zeolite Ywith a SAR of about 3.3 as determined by inductively coupled plasma(ICP) spectroscopy.

Example 2: ODSO as described in the Reference Example was added to thehomogeneous aqueous mixture used to synthesize zeolite Y to replace anapproximately equivalent amount of water as in the comparative Example1, at an ODSO/Na ratio of about 0.9. Ratios of other components areapproximately equivalent to those in the comparative Example 1. Aluminumisopropoxide (0.8676 g) was weighed into a PTFE liner (45 ml).Thereafter, 2.6662 g of a 50 wt. % sodium hydroxide solution, water(11.0680 g) and ODSO (0.7067 g) were added and the mixture was stirreduntil the aluminum source dissolved. The silica source, (3.1268 g, 40wt. %), was added and the mixture stirred until homogeneous. The mixturewas left to age for 24 hours at room temperature (20° C.) under constantstirring. The PTFE liner was positioned within an autoclave andtransferred to an oven and heated to a temperature of 100° C. whilstrotating the autoclave. The autoclave was kept at isothermal conditionsfor 12 hours. Thereafter, the product was washed with distilled waterand dried. The dry mass was 0.9429 g, and was determined to be zeolite Ywith a SAR of about 3.6 as determined by ICP spectroscopy.

Example 3: ODSO as described in the Reference Example was added to thehomogeneous aqueous mixture used to synthesize zeolite Y to replace anapproximately equivalent amount of water as in the comparative Example1, at an ODSO/Na ratio of about 1.5. Ratios of other components areapproximately equivalent to those in the comparative Example 1. Aluminumisopropoxide (0.8677 g) was weighed into a PTFE liner (45 ml).Thereafter, 2.6665 g of a 50 wt. % sodium hydroxide solution, water(10.5970 g) and ODSO (1.1770 g) were added and the mixture was stirreduntil the aluminum source dissolved. The silica source, (3.1265 g, 40wt. %), was added and the mixture stirred until homogeneous. The mixturewas left to age for 24 hours at room temperature (20° C.) under constantstirring. The PTFE liner was positioned within an autoclave andtransferred to an oven and heated to a temperature of 100° C. whilstrotating the autoclave. The autoclave was kept at isothermal conditionsfor 12 hours. Thereafter, the product was washed with distilled waterand dried. The dry mass was 0.9993 g, and was determined to be zeoliteY.

Example 4: ODSO as described in the Reference Example was added to thehomogeneous aqueous mixture used to synthesize zeolite Y to replace anapproximately equivalent amount of water as in the comparative Example1, at an ODSO/Na ratio of about 1.9. Ratios of other components areapproximately equivalent to those in the comparative Example 1. Aluminumisopropoxide (0.8675 g) was weighed into a PTFE liner (45 ml).Thereafter, 2.6617 g of a 50 wt. % sodium hydroxide solution, water(10.3620 g) and ODSO (1.4133 g) were added and the mixture was stirreduntil the aluminum source dissolved. The silica source, (3.1269 g, 40wt. %), was added and the mixture stirred until homogeneous. The mixturewas left to age for 24 hours at room temperature (20° C.) under constantstirring. The PTFE liner was positioned within an autoclave andtransferred to an oven and heated to a temperature of 100° C. whilstrotating the autoclave. The autoclave was kept at isothermal conditionsfor 12 hours. Thereafter, the product was washed with distilled waterand dried. The product was determined to be zeolite Y with a SAR ofabout 3.6 as determined by ICP spectroscopy.

FIG. 4 shows the x-ray diffraction patterns of the zeolites from theabove Examples (with the intensity level on the y-axis offset forclarity in the series of examples). It is clear from the peaks at thatzeolite Y has been produced in all cases from the peaks at about 6-50°(2 theta). The addition of ODSO to the sol-gel maintained the structuralintegrity of the (FAU) framework. Accordingly, it is demonstrated thatwhen (a) an ODSO-enhanced compositional ratio that is approximatelyequivalent to the baseline compositional ratio of silica source,aluminum source, alkali metal source and water is used, which is knownto be effective to produce faujasite zeolites including zeolite Y in theabsence of ODSO, and (b) wherein the conditions and time of heating theODSO-enhanced sol-gel is approximately equivalent to those that areeffective to produce the faujasite zeolites including zeolite Y in theabsence of ODSO, faujasite zeolites including zeolite Y are synthesized.For instance, in Example 1 herein (comparative), showing precursors thatproduce zeolite Y in the absence of ODSO, a baseline compositional ratioof Al₂O₃:SiO₂:Na₂O:H₂O on a molar basis is 1:10:8:400. In each of theExamples 2-4, approximately equivalent conditions, times and ratios wereused, except that an approximately equivalent mass of water was replacedwith an ODSO component, and hence the ODSO-enhanced compositional ratiois approximately equivalent to the baseline compositional ratio for theComparative Example 1.

Table 2 shows the normalized yield of zeolite Y as a function of ODSOaddition. It is clear that the ODSO addition increased the zeolite Yyield. FIG. 5 is a plot of ODSO/Na ratios against ODSO massdemonstrating transition between crystalline products and amorphousproducts, for products formed according to the examples herein, andother products with approximately equivalent ratios of precursors otherthan the ODSO substitution for water. The transition between crystallineproducts and amorphous products as a function of the ODSO/Na ratio isapparent.

As used herein, “approximately equivalent” as concerning the amount ofODSO that replaces water, the cumulative amount of ODSO and water, thecomponent molar or mass ratios, and/or the hydrolysis conditions andtime, is within a margin of less than or equal to plus or minus 1, 2, 5or 10% of the compared value.

It is to be understood that like numerals in the drawings represent likeelements through the several figures, and that not all components and/orsteps described and illustrated with reference to the figures arerequired for all embodiments or arrangements. Further, the terminologyused herein is for the purpose of describing particular embodiments onlyand is not intended to be limiting of the invention. As used herein, thesingular forms “a”, “an” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise. It willbe further understood that the terms “including,” “comprising,” or“having,” “containing,” “involving,” and variations thereof herein, whenused in this specification, specify the presence of stated features,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,integers, steps, operations, elements, components, and/or groupsthereof.

It should be noted that use of ordinal terms such as “first,” “second,”“third,” etc., in the claims to modify a claim element does not byitself connote any priority, precedence, or order of one claim elementover another or the temporal order in which acts of a method areperformed, but are used merely as labels to distinguish one claimelement having a certain name from another element having a same name(but for use of the ordinal term) to distinguish the claim elements.

Notably, the figures and examples above are not meant to limit the scopeof the present disclosure to a single implementation, as otherimplementations are possible by way of interchange of some or all thedescribed or illustrated elements. Moreover, where certain elements ofthe present disclosure can be partially or fully implemented using knowncomponents, only those portions of such known components that arenecessary for an understanding of the present disclosure are described,and detailed descriptions of other portions of such known components areomitted so as not to obscure the disclosure. In the presentspecification, an implementation showing a singular component should notnecessarily be limited to other implementations including a plurality ofthe same component, and vice-versa, unless explicitly stated otherwiseherein. Moreover, applicants do not intend for any term in thespecification or claims to be ascribed an uncommon or special meaningunless explicitly set forth as such. Further, the present disclosureencompasses present and future known equivalents to the known componentsreferred to herein by way of illustration.

The foregoing description of the specific implementations will so fullyreveal the general nature of the disclosure that others can, by applyingknowledge within the skill of the relevant art(s), readily modify and/oradapt for various applications such specific implementations, withoutundue experimentation, without departing from the general concept of thepresent disclosure. Such adaptations and modifications are thereforeintended to be within the meaning and range of equivalents of thedisclosed implementations, based on the teaching and guidance presentedherein. It is to be understood that the phraseology or terminologyherein is for the purpose of description and not of limitation, suchthat the terminology or phraseology of the present specification is tobe interpreted by the skilled artisan in light of the teachings andguidance presented herein, in combination with the knowledge of oneskilled in the relevant art(s). It is to be understood that dimensionsdiscussed or shown are drawings accordingly to one example and otherdimensions can be used without departing from the disclosure.

The subject matter described above is provided by way of illustrationonly and should not be construed as limiting. Various modifications andchanges can be made to the subject matter described herein withoutfollowing the example embodiments and applications illustrated anddescribed, and without departing from the true spirit and scope of theinvention encompassed by the present disclosure, which is defined by theset of recitations in the following claims and by structures andfunctions or steps which are equivalent to these recitations.

TABLE 1 ODSO Name Formula Structure Examples Dialkyl-sulfonesulfoxide Or1,2-alkyl-alkyl-disulfane 1,1,2-trioxide (R—SOO—SO—R′)

Dialkyl-disulfone Or 1,2 alkyl-alkyl-disulfane 1,1,2,2-tetraoxide(R—SOO—SOO—R′)

Alkyl-sulfoxidesulfonate (R—SO—SOO—OH)

Alkyl-sulfonesulfonate (R—SOO—SOO—OH)

Alkyl-sulfoxidesulfinate (R—SO—SO—OH)

Alkyl-sulfonesulfinate (R—SOO—SO—OH)

R and R′ can be the same or different alkyl or aryl groups comprising1-10 carbon atoms.

TABLE 2 ODSO/ Na Ratio Normalized (w/w) Yield 0 1.00 0.9 1.04 1.5 1.10An ODSO/Na ratio = 0 is a water-only synthesis in the absence of theODSO

1. A method for synthesis of faujasite zeolite comprising: forming ahomogeneous aqueous mixture of a silica source, an aluminum source, analkali metal source, water and an effective amount of water-solubleoxidized disulfide oil (ODSO); and heating the homogeneous aqueousmixture under conditions and for a time effective to form a precipitatesuspended in a supernatant as an intermediate suspension, wherein theprecipitate comprises faujasite zeolite.
 2. The method as in claim 1,wherein a cumulative amount of ODSO and water is approximatelyequivalent to an amount of water that is effective to produce faujasitezeolite in the absence of ODSO; the cumulative amount of ODSO and water,an amount of the silica source, an amount of the aluminum source, and anamount of the alkali metal source are provided at an ODSO-enhancedcompositional ratio; the ODSO-enhanced compositional ratio isapproximately equivalent to a baseline compositional ratio of water,silica, aluminum and alkali metal that is effective to produce faujasitezeolite in the absence of ODSO; and the conditions and time of heatingare approximately equivalent to those that are effective to producefaujasite zeolite in the absence of ODSO.
 3. The method of claim 1,wherein faujasite zeolite is recovered and is characterized by a zeoliteyield, and wherein the zeolite yield is greater than a zeolite yield fora comparable faujasite zeolite formed from the baseline compositionalratio of components.
 4. The method as in claim 1, wherein the faujasitezeolite is zeolite Y.
 5. The method as in claim 4, wherein the effectiveamount of ODSO is less than the amount of ODSO that produces onlyamorphous alumina or silica-alumina.
 6. The method as in claim 4,wherein the alkali metal source is sodium and the mass ratio of ODSO tosodium is in the range of about 0.1-2.5.
 7. The method as in claim 1,wherein the faujasite zeolite is zeolite X.
 8. The method as in claim 1,wherein the ODSO is derived from oxidation of disulfide oil compoundspresent in an effluent refinery hydrocarbon stream recovered followingcatalytic oxidation of mercaptans present in a mercaptan-containinghydrocarbon stream.
 9. The method as in claim 1, wherein the ODSOcompounds have 3 or more oxygen atoms and include one or more compoundsselected from the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR),wherein R and R′ are alkyl or aryl groups comprising 1-10 carbon atomsand wherein X denotes esters and is (R—SO) or (R—SOO).
 10. The method asin claim 1, wherein the ODSO compounds have 3 or more oxygen atoms andinclude two or more compounds selected from the group consisting of(R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR), wherein R and R′ are alkyl oraryl groups comprising 1-10 carbon atoms and wherein X denotes estersand is (R—SO) or (R—SOO).
 11. The method as in claim 1, wherein the ODSOcompounds have 3 or more oxygen atoms and include one or more compoundsselected from the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), wherein Rand R′ are alkyl or aryl groups comprising 1-10 carbon atoms.
 12. Themethod as in claim 1, wherein the aluminum source comprises aluminates,alumina, other zeolites, aluminum colloids, boehmites, pseudo-boehmites,aluminum hydroxides, aluminum salts, aluminum alkoxides, aluminum wireor alumina gels.
 13. The method as in claim 1, wherein the silica sourcecomprises sodium silicate (water glass), rice husk, fumed silica,precipitated silica, colloidal silica, silica gels, zeolites,dealuminated zeolites, silicon hydroxides or silicon alkoxides.
 14. Themethod as in claim 1, wherein crystallization occurs in the absence of aseed.
 15. (canceled)
 16. The method as in claim 1, whereincrystallization occurs in the presence of a seed and wherein the seed isselected from the group consisting of zeolite Y, zeolite X, USY zeolite,faujasite zeolite and small protozeolitic species (gels).
 17. The methodas in claim 1, wherein the pH of the intermediate suspension is in therange from about 9-14.
 18. The method as in claim 1, wherein thehomogeneous aqueous mixture is formed by: providing the silica source;and combining with the silica source the aluminum oxide source, thealkali metal source and the water-soluble ODSO; wherein thewater-soluble ODSO is added after the aluminum oxide source, the alkalimetal source, or wherein the water-soluble ODSO is first combined withthe aluminum oxide source and the alkali metal source, and then combinedwith the silica source; and wherein an effective amount of water for thehomogeneous aqueous mixture is provided by using utility water, awater-containing silica source, and/or by using an aqueous mixture ofthe aluminum oxide source and the alkali metal source.
 19. The method asin claim 1, wherein the homogeneous aqueous mixture is formed by:providing the aluminum oxide source and the alkali metal source as afirst mixture; and combining the first mixture with the silica sourceand the water-soluble ODSO; wherein the water-soluble ODSO is addedafter the silica source; or wherein the water-soluble ODSO is firstcombined with the silica source, and then combined with the firstmixture; and wherein an effective amount of water for the homogeneousaqueous mixture is provided by using utility water, a water-containingsilica source, and/or by using an aqueous mixture of the aluminum oxidesource and the alkali metal source.
 20. The method as in claim 1,wherein the homogeneous aqueous mixture is formed by: combining thewater-soluble ODSO with the silica source to form a first mixture; andcombining the first mixture with the aluminum oxide source and thealkali metal source; wherein an effective amount of water for thehomogeneous aqueous mixture is provided by using utility water, awater-containing silica source, and/or by using an aqueous mixture ofthe aluminum oxide source and the alkali metal source.
 21. The method asin claim 1, wherein the homogeneous aqueous mixture is formed by:combining the water-soluble ODSO with the aluminum oxide source and thealkali metal source to form a first mixture; and combining the firstmixture with the silica source; wherein an effective amount of water forthe homogeneous aqueous mixture is provided by using utility water, awater-containing silica source, and/or by using an aqueous mixture ofthe aluminum oxide source and the alkali metal source.